Electrochromic organic polymer synthesis and devices utilizing electrochromic organic polymers

ABSTRACT

Large contrast ratio and rapid switching laminated electrochromic (EC) polymer device includes transparent electrode, cathodic EC polymer, gel electrolyte, and counter-electrode. Preferably the cathodic EC polymer is a poly(3,4-propylenedioxythiophene) derivative, PProDOT-Me 2 . Counter-electrode is a conductive coating deposited on transparent substrate, with preferred coatings including gold and highly conductive carbon. Lithography and sputtering can be employed to pattern a gold layer, while screen printing can be employed to similarly pattern graphite. Empirical studies of preferred device indicate a color change of high contrast ratio of transmittance (&gt;50% T) is rapidly (0.5-1s) obtained upon applied 2.5V, repeatable to at least 10,000 times, as estimated by electrochemistry. Dual layer EC devices including PProDOT-Me 2  are also disclosed, as are methods for synthesizing preferred EC polymers. Preferred synthesis method for obtaining PProDOT-Me 2  involves refluxing reagents in toluene in the presence of catalyst, while continually removing methanol byproduct from refluxing solution.

RELATED APPLICATIONS

[0001] This application is based on three prior copending provisional applications, including Ser. No. 60/300,675, filed on Jun. 25, 2001, Ser. No. 60/324,205, filed on Sep. 21, 2001, and Ser. No. 60/364,418, filed on Mar. 14, 2002, the benefits of the filing dates of which are hereby claimed under 35 U.S.C. § 119(e).

FIELD OF THE INVENTION

[0002] The present invention generally relates to electrochromic (EC) materials that exhibit different colors as a function of an applied voltage, and more specifically, to apparatus utilizing specific organic polymer based EC materials, and methods of producing the specific organic polymer based EC materials.

BACKGROUND OF THE INVENTION

[0003] Electrochromic (EC) materials are a subset of the family of chromogenic materials, which includes photochromic materials, and thermochromic materials. These are materials that change their tinting level or opacity when exposed to light (photochromic), heat (thermochromic) or electricity (electrochromic). Chromogenic materials have attracted widespread interest in applications relating to the transmission of light.

[0004] An early application for chromogenic materials was in sunglasses or prescription eyeglasses that darken when exposed to the sun. Such photochromic materials were first developed by Coming in the late 1960s. Since that time, it has been recognized that chromogenic materials could potentially be used to produce window glass that can vary the amount of light transmitted, although the use of such materials is clearly not limited to that prospective application. Indeed, EC technology is already employed in the displays of digital watches.

[0005] With respect to window glass, EC materials are exciting because they require relatively little power to produce a change in their tinting level or opacity. EC windows have been suggested for use in controlling the amount of daylight and solar heat gain through the windows of buildings and vehicles. Early research indicates that EC window technology can save substantial amounts of energy in buildings, and EC glazings may eventually replace traditional solar control technology such as tints, reflective films, and shading devices (e.g., awnings). Because of their ability to control lighting levels and solar heat gain, EC windows have the potential of reducing the annual U.S. energy consumption by several quadrillion (10¹⁵) BTUs, or quads, which is a substantial decrease relative to current consumption rates.

[0006] Several different distinct types of EC materials are known. The primary three types are inorganic thin films, organic polymer films, and organic solutions. For many applications, the use of a liquid material is inconvenient, and as a result, inorganic thin films and organic polymer films appear to be more industrially applicable.

[0007] To make an EC device that exhibits different opacities in response to a voltage, a multilayer assembly is required. In general, the two outside layers of the assembly are transparent electronic conductors. Within the outside layers is a counter-electrode layer and an EC layer, between which is disposed an ion conductor layer. When a low voltage is applied across the outer conductors, ions moving from the counter-electrode to the EC layer cause the assembly to change color. Reversing the voltage moves ions from the EC layer back to the counter-electrode layer, restoring the device to its previous state. Of course, all of the layers are preferably transparent to visible light. Both inorganic and organic ion conductive layers are known.

[0008] In order to be useful in a window application, or in a display application, EC materials must exhibit long-term stability, rapid redox switching, and exhibit large changes in opacity with changes of state. For inorganic thin film based EC devices, the EC layer is typically tungsten oxide (WO₃). U.S. Pat. Nos. 5,598,293, 6,005,705, and 6,136,161 each describe an inorganic thin film EC device based on a tungsten oxide EC layer. Other inorganic EC materials, such as molybdenum oxide, are also known. While many inorganic materials have been used as EC materials, difficulties in processing and slow response time associated with many inorganic EC materials have created the need for different types of EC materials.

[0009] Conjugated, redox-active polymers represent one different type of EC material. These polymers (cathodic or anodic polymers) are inherently electrochromic and can be switched electrochemically or chemically between different color states. A family of redox-active copolymers are described in U.S Pat. No. 5,883,220. Another family of nitrogen based hetrocyclic organic EC materials is described in U.S Pat. No. 6,197,923. Research into still other types of organic film EC materials continues, in hopes of identifying or developing EC materials that will be useful in EC windows.

[0010] While EC windows, or smart windows as they are sometimes called, are expected to represent a significant commercial application of EC technology, one additional potential use of an EC is in producing displays, sometimes referred to smart displays, or digital windows (DWs). One promising application for DW systems relates to deoxyribonucleic acid (DNA) chip reading. For more efficient DNA chip reading/writing technology, it would be desirable to replace expensive custom photomasks in the photosynthesizing of oligonucleotides in DNA array fabrication. There are several reasons why it would be desirable to develop a new method applicable to this technology for use in oligonucleotide chip manufacturing. Specifically, oligonucleotide chips have become increasingly important, as more genomes of organisms are sequenced. Accordingly, there is a need to develop a low cost, easy to use, high-density DNA arranger and system for reading unknown DNAs, based on surface plasmon resonance, with higher lateral resolution that is provided in current systems.

[0011] A suitable system for such an application should employ a switchable window that is readily changed from transparent to nontransparent (e.g., to dark blue) by varying an electric potential polarity (anodic EC polymer sides have a negative polarity and a positive polarity, respectively). These switchable window laminate materials should be convertible to a digital (pixel) array having a size typically ranging from about submicron to about 50 microns, and each array unit should be independently controlled to change from a transparent to a nontransparent state. By combining this functionality with an surface plasmon resonance (SPR) system serving as a real time analyzer of unknown molecules, including DNA sequences and characterizations of unknown molecules and in vivo and in vitro cell-cell interactions. Such a high resolution SPR system should then be useful for analyzing unknown molecules and DNA sequences on a real-time basis, at faster speed than is currently possible, by scanning through one group of molecules after another, i.e., by opening the corresponding digital window (DW) unit. With such a system, the speed with which unknown molecules (and DNA and RNA sequences) can be analyzed will be much enhanced, compared with conventional prior art techniques.

[0012] An additional exciting application of EC technology relates to the use of EC devices for display technologies, beyond the somewhat limited application of monochromatic displays now used in digital watches. EC devices that can controllably transition between more than two color states offer the potential of flat panel multicolor displays, using the digital pixel array noted above.

SUMMARY OF THE INVENTION

[0013] A first aspect of the present invention is directed to a method for synthesizing EC polymers and counter-electrodes having properties that can be beneficially employed in EC polymer devices. A second aspect of the present invention is directed to specific configurations of EC polymer based devices, while a third aspect is directed to specific applications of EC polymer devices. With respect to synthesizing EC polymers and counter-electrodes, two embodiments of the method for synthesizing EC polymers is disclosed, as well as two embodiments for fabricating counter-electrodes for use in EC devices.

[0014] The first synthesis method is directed toward the production of poly[3,3-dimethyl-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepine], also known as PProDOT-Me ₂. Preferably, equivalent molar amounts of 3,4-dimethoxythiophene and 2,2-dimethyl-1,3-propanediol are dissolved in toluene and heated in the presence of p-toluenesulfonic acid monohydrate (at a concentration of 1.5 mol % of 3,4-dimethoxythiophone) and left for 10-20 hours at a temperature of 110° C. Those of ordinary skill in the art will recognize that the specified temperature is the boiling point of toluene. The toluene is heated to boiling, toluene vapors are collected and condensed, and then returned to the original solution (i.e. the solution of 3,4-dimethoxythiophene, 2,2-dimethyl-1,3-propanediol, toluene and p-toluenesulfonic acid monohydrate). This process is referred to in the chemical arts as refluxing.

[0015] A methanol byproduct is produced during the synthesis, and that methanol byproduct significantly reduces the rate of the reaction. Preferably, the synthesis includes the step of removing the methanol byproduct by absorbing it with calcium chloride. This can be achieved by treating the condensed toluene vapors with calcium chloride before returning the condensed toluene vapors to the original boiling solution. This will remove the methanol byproduct from the condensed toluene vapors. As those of ordinary skill in the art will recognize, such a “salting out” process is sometimes employed in organic synthesis to remove undesirable reactants.

[0016] A second organic polymer expected to be useful in EC devices is poly[3,6-bis(2-(3,4ethylenedioxythiophene))-N-methylcarbazole, also known as PBEDOT-NMeCz. This synthesis is somewhat more involved, requiring the formation of two intermediate compounds from readily available reagents. The intermediate compounds are then reacted in the presence of catalyst to obtain the desired product. To obtain a first intermediate compound, poly(3,4-ethylenedioxythiophene) (EDOT) is treated with n-butyl lithium in a solution of tetrahydrofuran (THF) at −78° C. for one hour. The resulting intermediate compound, a Grignard reagent, is then treated with magnesium bromide diethyl etherate. That brominated intermediate product is temporarily stored in the THF solvent.

[0017] The next intermediate compound is obtained by combining dibromocarbazole (C₁₂H₆Br₂NH) with lithium hydride (LiH) in dimethyl foramide (DMF), maintained at less than 10° C. for an hour. That intermediate compound is methylated (preferably using methyl iodine, MeI or CH₃I), and the temperature is raised to 50° C. over a two hour period, yielding a methylated dibromocarbazole (Cl₂H₆Br₂NCH₃) intermediate product. This intermediate product is preferably purified by washing with water and ether and dried over sodium sulfate.

[0018] The two intermediate products are combined in the presence of a nickel catalyst, resulting in the EDOT rings being affixed to the derivatized dibromocarbazole. The reaction is facilitated by maintaining the mixture of the two intermediate products at 50° C. over a twelve hour period, to yield BEDOT-NMeCz.

[0019] A first embodiment of a counter-electrode useful for EC devices can be produced by placing a thin layer of gold on a glass substrate. Preferably, the thickness of the substrate is on the order of 0.7 mm, with the gold layer being no thicker, and preferably, substantially thinner. A layer of titanium-tungsten (TiW) may be added to the glass substrate first to enhance the gold bond to the substrate. Preferably, less than 25 percent of the substrate surface is covered with the gold layer, which is deposited in a pattern that enhances conductivity across most of the surface area of the counter-electrode. Preferably the pattern includes continuous lines, such as may be achieved in a grid pattern.

[0020] A second embodiment of a counter-electrode useful for EC devices can be produced by replacing the thin layer of gold with a thin layer of highly conductive carbon, such as graphite. The TiW layer is then not required. It is preferred to include an indium tin oxide layer between the glass and the graphite.

[0021] In regard to laminated EC devices made up of at least one EC polymer, one embodiment includes both a cathodic EC polymer layer and an anodic EC polymer layer. A different embodiment utilizes a cathodic EC polymer layer and a counter-electrode layer. The embodiment utilizing two EC polymer layers includes transparent electrodes as both top and bottom layers. Indium tin oxide coated glass comprises a preferred transparent electrode. Under the top transparent electrode is disposed the cathodic EC polymer layer. A preferred cathodic polymer is PProDOT-Me₂. Adjacent to the cathodic polymer layer is disposed a solid electrolyte layer. A preferred solid electrolyte comprises a gel electrolyte, having a polymer matrix, a solvent carrier, and an ion source. Lithium perchlorate (LiClO₄) is a preferred ion source. One preferred gel electrolyte is polyvinyl chloride (PVC) based and another preferred electrolyte is polymethyl metracrylate (PMMA) based; both contain LiClO₄. The next layer of the device comprises the anodic polymer layer, preferably comprising PBEDOT-NMeCz. A final layer comprises the transparent electrode layer noted above. In the oxidized state, when no voltage (or a positive voltage) is applied, both polymer layers are substantially clear and have a high transmittance. It should be noted however, that the PBEDOT-NMeCz never achieves a completely colorless state. When a negative voltage is applied, each EC polymer layer undergoes a reduction and changes in color from nearly transparent to dark blue. The PProDOT-Me₂ layer attains a darker tint, and is thus more opaque. The color change of the device is very rapid (about 0.5˜1 s) and repeatable (more than 10,000 times).

[0022] The embodiment of the EC device that has only a single EC polymer layer also includes a transparent electrode as a top layer. Again, indium tin oxide coated glass comprises a preferred transparent electrode. Examples of transparent electrodes are ITO and doped zinc oxide films deposited on transparent substrates, such as glass or plastics. After transparent electrode layer is the cathodic EC polymer layer, preferably PProDOT-Me₂, followed by a solid electrolyte layer of the type described above. Adjacent to and following the solid electrolyte layer is a counter-electrode layer. A preferred counter-electrode layer includes a conductive coating applied to a transparent substrate (such as glass or plastic). Preferably, the conductive coating does not reduce transmittance through the counter-electrode layer by more than 25 percent. Preferred conductive coatings are gold and graphite, deposited in a pattern that substantially covers the substrate. A preferred pattern includes continuous lines, such as found in a grid. In the oxidized state, when no voltage negative (or a positive voltage) is applied, the PProDOT-Me₂ polymer layers is substantially clear, with very little tint. When a negative voltage is applied, the counter-electrode enhances the speed with which the PProDOT-Me₂ polymer layers undergoes a reduction and changes in color from nearly transparent to dark blue. The color change of the device is very rapid (about 0.5˜1 s) and repeatable (more than 10,000 times).

[0023] A first preferred application specific embodiment comprises a smart window that is able to change state from substantially transparent when no voltage (or a positive voltage) is applied, to substantially opaque when a negative voltage is applied. A first embodiment of the smart window is based on a dual polymer EC device, which includes a PProDOT-Me₂ cathodic polymer layer, a solid electrolyte layer, and a PBEDOT-NMeCz anodic polymer layer, as described above. A second embodiment of the smart window is based on a single polymer EC device, utilizing a PProDOT-Me₂ cathodic polymer layer, a solid electrolyte layer, and a counter-electrode layer, also substantially as described above.

[0024] Still another application specific embodiment is directed to a DW for DNA chip and unknown molecules reading technology based on SPR imaging with high lateral resolution. Currently, DNA chip reading/writing technology requires expensive custom photomasks used in the photosynthesizing of oligonucleotides in DNA array fabrication. In this embodiment of the present invention, a DW including a plurality of individually addressable pixels arranged in a grid format is employed in the place of the conventional photomask. A voltage can be applied to each pixel individually, enabling selective masking to be achieved.

BRIEF DESCRIPTION OF THE DRAWING FIGURES

[0025] The foregoing aspects and many of the attendant advantages of this invention will become more readily appreciated as the same becomes better understood by reference to the following detailed description, when taken in conjunction with the accompanying drawings, wherein:

[0026]FIG. 1A is a schematic illustration of the synthesis of the monomer ProDOT-Me₂, which when polymerized may be beneficially employed as a cathodic EC polymer;

[0027]FIG. 1B is a schematic illustration of apparatus used in the synthesis of FIG. 1A;

[0028]FIG. 2 schematically illustrates the synthesis of the monomer BEDOT-NMeCz, which may be beneficially employed as an anodic EC polymer once it has been polymerized;

[0029]FIGS. 3A and 3B are side elevational schematic illustrations of an EC device that includes a cathodic (PProDOT-Me₂) EC polymer film, an anodic (PBEDOT-NMeCz) EC polymer film, and a solid electrolyte layer;

[0030]FIGS. 4A and 4B are side elevational schematic illustrations of an EC device that includes a cathodic EC polymer film, a solid electrolyte layer and a counter-electrode;

[0031]FIG. 5A is a plan view of a gold based counter-electrode being fashioned from a glass wafer;

[0032]FIG. 5B is a plan view of a gold based counter-electrode;

[0033]FIG. 5C is a side elevational view of a gold based counter-electrode;

[0034]FIGS. 6A and 6B illustrate alternative patterns that can be used to form a conductive layer on a counter-electrode;

[0035]FIG. 7A is a plan view of a graphite based counter-electrode;

[0036]FIG. 7B is a side elevational view of a graphite based counter-electrode;

[0037]FIG. 8A schematically illustrates a working model of a smart window including a PProDOT-Me₂ cathodic polymer film layer and a counter-electrode layer, to which either no voltage or a positive voltage is being applied, thus the smart window is in the oxidized or transparent state;

[0038]FIG. 8B schematically illustrates the working model of FIG. 8A, to which a negative voltage is being applied, thus the smart window is in the reduced or opaque state;

[0039]FIG. 9A graphically illustrates the repeatability of a color change in an EC device containing a PProDOT-Me₂ cathodic polymer film and a counter-electrode, in response to changes in applied voltage;

[0040]FIG. 9B graphically illustrates the repeatability of color changes in an EC device containing a PProDOT-Me₂ cathodic polymer film and a PBEDOT-NMeCz EC polymer film, in response to changes in applied voltage;

[0041]FIG. 10A graphically illustrates the transmittance of an EC device containing a PProDOT-Me₂ cathodic polymer film and a gold based counter-electrode in the UV-visible spectrum;

[0042]FIG. 10B graphically illustrates the transmittance of an EC device containing a PProDOT-Me₂ cathodic polymer film and a graphite based counter-electrode in the UV-visible spectrum;

[0043]FIG. 11A graphically illustrates the optical switching abilities of an EC device containing a PProDOT-Me₂ cathodic polymer film and a gold based counter-electrode, based on absorbance versus time;

[0044]FIG. 11B graphically illustrates the optical switching abilities of an EC device containing a PProDOT-Me₂ cathodic polymer film and a graphite-based counter-electrode, based on absorbance versus time;

[0045]FIG. 12 graphically illustrates that the time response of an EC device containing a PProDOT-Me₂ cathodic polymer film and a gold based counter-electrode is substantially the same even at different potentials;

[0046]FIG. 13 graphically illustrates that the opacity of an EC device containing a PProDOT-Me₂ cathodic polymer film and a gold based counter-electrode is a function of an applied potential;

[0047]FIG. 14A graphically illustrates the consistent repeatability of a current vs. time relationship for an EC device containing a PProDOT-Me₂ cathodic polymer film and a gold based counter-electrode;

[0048]FIG. 14B graphically illustrates the consistent repeatability of a current vs. time relationship for an EC device containing a PProDOT-Me₂ cathodic polymer film and a graphite-based counter-electrode;

[0049]FIG. 15A graphically illustrates the temperature dependence of an EC device containing a PProDOT-Me₂ cathodic polymer film and a gold based counter-electrode, and an EC device containing a PProDOT-Me₂ cathodic polymer film and a graphite-based counter-electrode, indicating that changes in temperature do not have a significant effect on the current within such devices;

[0050]FIG. 16 illustrates use of a DW for DNA chip reading technology based on SPR imaging with high lateral resolution digital window;

[0051]FIG. 17 is a schematic illustration of the EC devices of the present invention being integrated into a conventional dual pane architectural window; and

[0052]FIG. 18 schematically illustrates the operation of a cathodic polymer EC layer paired to a counter-electrode layer.

DESCRIPTION OF THE PREFERRED EMBODIMENT

[0053] The present invention is directed to methods for synthesizing EC polymers having properties that can be beneficially employed in an EC polymer device, specific configurations of EC polymer based devices, and specific applications of EC polymer devices. First, the synthesis of the EC polymers will be discussed, followed by a description of specific configurations for an EC device, and finally, specific applications of an EC device will be described. For those not familiar with the workings of EC devices, an overview has been provided at the end of this description.

[0054] Synthesis of EC Polymers

[0055] A first organic polymer expected to be useful in EC devices is poly[3,3-dimethyl-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepine], also known as dimethyl substituted poly(3,4-propylenedioxythiophene), or PProDOT-Me₂. FIG. 1A illustrates the preferred transetherification reaction 10 for the preparation of ProDOT-Me₂. 3,4-dimethoxythiophene and 2,2-dimethyl-1,3-propanediol are dissolved in toluene and heated in the presence of p-toluenesulfonic acid monohydrate (at a concentration of 1.5 mol % of 3,4-dimethoxythiophene) for 10-20 hours at a temperature of 110° C. This process is referred to in the chemical arts as refluxing, as at a temperature of 110° C. toluene boils. In a refluxing process, a solution is boiled until a fraction of the solution (in this case the toluene fraction, as the 3,4-dimethoxythiophene, the 2,2-dimethyl-1,3-propanediol and the p-toluenesulfonic acid monohydrate fractions each have higher boiling points) is driven out of the solution as a vapor, and those vapors are then condensed and returned to the original solution.

[0056] The purpose of employing refluxing in the present invention is because methanol is produced as an undesirable byproduct when 3,4-dimethoxythiophene and 2,2-dimethyl-1,3-propanediol combine to form the desired product. Once some of the 3,4-dimethoxythiophene and 2,2-dimethyl-1,3-propanediol combine to form the desired product, the presence of the methanol byproduct actually inhibits further reaction between the3,4-dimethoxythiophene and 2,2-dimethyl-1,3-propanediol. Thus to increase the amount of desired product that can be produced, the methanol byproduct is preferably removed as it is generated. Refluxing enables the methanol byproduct to be continually removed. Both methanol and toluene have boiling points that are lower than the boiling points of the other fractions; 3,4-dimethoxythiophene, 2,2-dimethyl-1,3-propanediol, p-toluenesulfonic acid monohydrate and the desired product. By heating the toluene to boiling, both the methanol and toluene are removed from the solution. The removed toluene and methanol are condensed and collected in a separate container. Calcium chloride is added to that separate container, which reacts with the methanol to enable the methanol to be removed from the toluene. The condensed toluene then is returned to the original solution (the boiling 3,4-dimethoxythiophene, 2,2-dimethyl-1,3-propanediol, p-toluenesulfonic acid monohydrate, toluene and the desired product). Thus a preferable step in the synthesis is removing the methanol using calcium chloride. As those of ordinary skill in the art will recognize, such a “salting out” process is sometimes employed in organic synthesis to remove undesirable reactants. In one embodiment, the condensed methanol and condensed toluene are filtered through solid calcium chloride. The resulting monomer, ProDOT-Me₂, is readily polymerized to PProDOT-Me₂.

[0057]FIG. 1B schematically illustrates an apparatus 11 used to perform the above synthesis. The reactants (3,4-dimethoxythiophene, 2,2-dimethyl-1,3-propanediol, and p-toluenesulfonic acid monohydrate) are dissolved in toluene in a container 13. Sufficient heat is applied to container 13 (as noted above the boiling point of toluene is 110° C., and while the reagents added to the toluene will somewhat affect the boiling point of the solution, the boiling point of the solution will still be substantially 110° C.) so that the solution within the container gently boils. Toluene vapor (and any methanol byproduct) will be driven out of container 13 and into boiling tube 15. The vapors will rise into condenser 17, where the vapors cool and fall into packed calcium chloride 19. The movement of the vapors is indicated by a dashed line, while the movement of the condensed vapors is indicated by solid lines. The methanol is absorbed by the calcium chloride, and the condensed toluene rises to a level 21, where the condensed toluene returns back to container 13 via boiling tube 15. Preferably the amount of toluene employed, and the internal volume of apparatus 11 is such that some toluene always remains within container 13 (i.e. the solution never completely boils away) and that the condensed toluene is able to rise through the packed calcium chloride to level 21, such that some condensed toluene returns to container 13. Preferably a nitrogen blanket is introduced into apparatus 11, so that ambient oxygen does not introduce undesired byproducts or cross reactions.

[0058] A second organic polymer expected to be useful in EC devices is poly[3,6-bis(2-(3,4ethylenedioxythiophene))-N-methylcarbazole, also known as PBEDOT-NMeCz. A preferred synthesis scheme 30 is shown in FIG. 2. First, (3,4-ethylenedioxythiophene) (EDOT) is treated with n-Butyl lithium in a solution of tetrahydrofuran (THF) at −78° C. for one hour. Those of ordinary skill in the art will recognize this step as that employed in the preparation of a Grignard reagent. The resulting Grignard reagent is then treated with magnesium bromide diethyl etherate. The product (i.e., the reagent B), remains in the THF solvent.

[0059] Then, a derivatized dibromocarbazole is combined with lithium hydride in dimethyl foramide (DMF) and kept at less than 10° C. for an hour. Methyl groups are slowly added at a 1:1 ratio, and the temperature is raised to 50° C. over a two hour period, yielding a methylated derivatized dibromocarbazole product (i.e., the reagent C), which is purified by washing with water and ether, and dried over sodium sulfate. Preferably methyl iodine (MeI) is used as a methylating agent. Reagents B and C are combined, resulting in the EDOT rings being affixed to the derivatized dibromocarbazole. The reaction between B and C is facilitated with a nickel catalyst, and requires that the reagents be held together at 50° C. over a twelve hour period, to yield BEDOT-NMeCz. The BEDOT-NMeCz monomer may then be polymerized to obtain the PBEDOT-NMeCz polymer to be used as an anodic layer in an ED device.

[0060] EC Device Configurations

[0061] Another aspect of the present invention is directed at specific configurations of EC devices utilizing EC polymers. Each configuration disclosed herein is based on a laminated system, including at least one EC polymer, a solid or liquid electrolyte, and upper and lower layers of transparent electrodes.

[0062] A first configuration for an EC device is schematically illustrated in both a transparent state 40 a in FIG. 3A, and a colored state 40 b in FIG. 3B. Note that structurally, there is no difference in the EC device in either the transparent state or the colored state. When a voltage is applied to the EC device, the EC polymers of the cathode and anode layers undergo a color change. The first configuration, as collectively illustrated in FIGS. 3A and 3B, thus includes a cathodic (PProDOT-Me₂) EC polymer layer and an anodic (PBEDOT-NMeCz) EC polymer layer. It should be noted that the polarity of the applied voltage is important. If a positive voltage is applied, the EC polymers of the present invention will either stay in the bleached state (assuming there was no negative voltage applied immediately prior to applying the positive voltage), or transition from the opaque state to the bleached state (assuming there was a negative voltage applied immediately prior to applying the positive voltage). If a negative voltage is applied, the EC polymers of the present invention will either stay in the opaque state (assuming there already was a negative voltage being applied immediately prior to applying additional negative voltage), or transition from the bleached state to the opaque state (assuming there was either a positive voltage applied immediately prior to applying the negative voltage, or no voltage applied immediately prior to applying the negative voltage).

[0063] A top layer is a transparent electrode 42, preferably formed from an indium tin oxide (ITO) coated transparent substrate. While an ITO film on a transparent substrate represents a preferred transparent electrode, it should be understood that other materials, such as tungsten oxide and doped zinc oxide films over transparent substrates, can be beneficially employed as a transparent electrode. It should also be understood that while glass certainly represents a preferred transparent substrate, that other transparent materials, such as plastics and polymers, can also be beneficially employed as a transparent substrate. Thus the use of the term glass substrate should be considered to be exemplary, rather than limiting the scope of the present invention. The next layer is a cathodic PProDOT-Me₂) EC polymer layer, which in FIG. 3A is shown as a transparent layer 44 a, and in FIG. 3B is shown as a colored layer 44 b. It should be understood that when no voltage (or a positive voltage) is applied, the PProDOT-Me₂ EC polymer layer is not completely colorless. Instead, a light blue tint can be discerned (hence the shading in transparent layer 44 a of FIG. 3A). As a negative voltage is applied, the PProDOT-Me₂ EC polymer layer becomes progressively more opaque, until it reaches saturation (a dark blue tint, as indicated by the shading in colored layer 44 b of FIG. 3B).

[0064] Following the cathode EC polymer layer is a solid/gel electrolyte layer 46. The solid/gel electrolyte layer is followed by anodic (PBEDOT-NMeCz) EC polymer layer 48, which is also illustrated as being a transparent layer 48 a in FIG. 3A, and a colored layer 48 b in FIG. 3B. Note that even with no voltage applied (or a positive voltage is applied), PBEDOT-NMeCz is not colorless, and a definite yellowish tint is apparent (hence, the shading in transparent layer 48 a of FIG. 3A). Again, as a negative voltage is applied, the PBEDOT-NMeCz EC polymer layer becomes progressively more opaque, until it reaches saturation (a moderate blue tint, as indicated by the shading in colored layer 44 b of FIG. 3B). The PBEDOT-NMeCz EC polymer layer is followed by a bottom layer, which is an additional transparent electrode 42, also preferably formed from indium tin oxide (ITO) coated glass.

[0065] The first configuration (FIGS. 3A and 3B) provides a dual EC polymer device, in which the darkness (or opacity) of colored state is increased by using two EC polymers. However, the transmittance of the bleached state is decreased, primarily because the anodic polymer has a noticeable tint in the transparent (or bleached) state. The monomer (e.g., BEDOT-NMeCz) used to generate the anodic EC polymer (e.g., PBEDOT-NMeCz) is somewhat difficult to synthesize, although the present invention does encompass a method for its synthesis.

[0066] The cathodic layer, which is based on a poly(3,4-propylenedioxythiophene) derivative (PProDOT-Me₂), expresses an excellent light transmittance change of 78 percent between the bleached and unbleached states. PProDOT-Me₂ exhibits rapid switching, low oxidation potentials, and excellent stability at ambient and elevated temperature.

[0067] In an EC device, the electrolyte layer must be ionically conductive, but electrically insulating. Both poly(vinyl chloride) (PVC) based and polymethylmetracrylate (PMMA) based gel electrolytes containing lithium perchlorate (LiClO₄) can be employed for solid electrolyte layer 46. Preferably, solid electrolyte layer 48 is fabricated from PVC (or PMMA), propylene carbonate (PC), ethylene carbonate (EC) and LiClO₄. The PVC (or PMMA) electrolyte mixture is dissolved in tetrahydrofuran (THF). Either PVC or PMMA based gel electrolytes provide high conductivity (2 mS/cm) at room temperature.

[0068] In such a gel electrolyte, the solid polymer matrix of PVC and PMMA provide dimensional stability to the electrolyte, while the high permittivity of the solvents EC and PC enable extensive dissociation of the lithium salts. The low viscosity of EC and PC provides an ionic environment that facilitates high ionic mobility.

[0069] Another useful gel electrolyte can be prepared from 3% LiClO₄, 7% PMMA, 20% PC and 70% acetonitrile (ACN) (% by weight). A simple synthesis of such a gel is achieved by first dissolving the PMMA and LiClO₄ in ACN. PC was dried over 4 angstrom molecular sieves and then combined with the other ingredients. The complete mixture was stirred for 10-14 hours at room temperature. A high conductivity (2 mS/cm), high viscosity and transparent gel electrolyte was formed. As described above, the solid polymer matrix of PMMA provides dimensional stability to the electrolyte, while the high permittivity of the solvents PC and ACN enable extensive dissociation of the lithium salt. The low viscosity of PC provides an ionic environment that facilitates high ionic mobility.

[0070] While gel electrolytes are preferred because they facilitate the production of a solid state device (the solvent liquid is contained within the polymer matrix), liquid electrolytes can be used in an EC device. One such liquid electrolyte can be achieved using 0.1M Tetrabutylammonium perchlorate (TBAP) in ACN. It is contemplated that materials other than PVC and PMMA can be employed to provide a polymer matrix for a gel electrolyte, and that materials other than TBAP and LiClO₄ can be employed as ionic sources.

[0071] A second preferred configuration for an EC device is similarly schematically illustrated in both a transparent state 50 a in FIG. 4A, and a colored state 50 b in FIG. 4B. Again, from a structural standpoint, there is no difference in the EC device in either the transparent state or the colored state. The second configuration, as collectively illustrated in FIGS. 4A and 4B, includes a cathodic PProDOT-Me₂ EC polymer layer and a counter electrode layer, but no anodic PBEDOT-NMeCz EC polymer layer. As before, the polarity of the voltage applied is critical in determining how such devices will respond.

[0072] Again, the top layer is transparent electrode 42, again, preferably ITO. The next layer is a cathodic PProDOT-Me₂ EC polymer layer, which in FIG. 4A is shown as a transparent layer 44 a, and in FIG. 4B is shown as a colored layer 44 b. After the cathode EC polymer layer comes a solid/gel electrolyte layer 46. The solid electrolyte layer is followed by a counter-electrode layer 52. No bottom transparent electrode layer is required.

[0073] Counter-electrode layer 52 is preferably gold based, platinum based, or highly conductive carbon based, and replaces the anodic EC polymer and bottom ITO electrode utilized in the first configuration described above. A preferred highly conductive carbon is graphite. It should be understood that while graphite certainly represents a preferred highly conductive carbon, that other highly conductive carbon materials can also be beneficially employed as a conductive film to be coated onto a transparent substrate to produce a counter-electrode. Many types of conductive carbons are available from a variety of manufacturers, such as Tokai Carbon Co. of Tokyo, Japan; and LORESCO INTERNATIONAL, of Hattiesburg, Miss. Thus the use of the term graphite herein should be considered to be exemplary, rather than limiting the scope of the present invention. It is further contemplated that nickel can be beneficially employed as a conductive film on a transparent substrate to produce a counter-electrode. The use of a counter-electrode can improve the speed of the color change between states, as well as the high contrast ratio between the two states. The counter-electrode material should be chemically stable, provide high electrical conductivity, and should be easy to fashion into a patterned substrate. Gold, highly conductive carbons, and platinum have been identified as being electrically conductive materials that can be beneficially employed for making a counter-electrode. It is contemplated that graphite will be very useful because of its low cost, and gold, while much more expensive, can be used in very thin layers, thereby minimizing the cost of a gold based counter-electrode. Platinum, while electrically conductive, is likely to be so expensive as to preclude its use. It is further contemplated that other conductive materials can be employed to produce the counter-electrode.

[0074] A gold based counter-electrode was produced as described below, and is illustrated in FIGS. 5A-5C. Polished float glass, 0.7 mm thick (available from Delta Technologies, Limited), was used as a substrate. The glass was cut into a 4 inch diameter glass wafer 56. Lithography and sputtering techniques were used for forming a gold pattern 58 on the glass wafer. Optionally, before the gold coating was applied, a layer 60 of titanium-tungsten (TiW) was first sputtered onto the glass substrate. TiW layers have often been used as barrier layers and capping layers in semiconductor manufacturing. The TiW layer helps tightly bind the gold layer to the glass substrate. The pattern design, or pattern geometry, ultimately effects the EC device. The wider the lines of conductive material on the counter-electrode, and the larger open areas of the patterning are expected to provide higher conductivity, thus enhancing the speed of the color change of the EC polymer, at the cost of decreasing transmittance through the counter-electrode when no voltage (or a positive voltage) is applied. Note that for some applications, particularly windows, transmittance through the EC device is very important. If the maximum transmittance through the EC device (or through any part of the device, such as the counter-electrode) is reduced to an unacceptable level, then the device may not be suitable for use in an application such as a window. The checkerboard pattern shown in FIGS. 5A and 5B offers a pattern that, when sufficiently small, is substantially transparent. It is contemplated that as an alternative to the square orifices in the gold layer, circular orifices or diamond shaped orifices would be equally useful, as respectively shown in FIGS. 6A and 6B. Preferably, less than 25 percent of the glass substrate is covered with gold, in order to maintain high transmittance. It should be noted that transmittance is maximized when the total area of the layer of gold (or graphite) is minimized, while conductivity is maximized when the area of the layer of gold (or graphite) is maximized. If an EC device must have excellent transmittance, and a somewhat slower response time is acceptable, then the percentage of the counter-electrode surface area devoted to a gold or graphite layer can be decreased. On the other hand, if response time is more important than transmittance, then the percentage of the counter-electrode area devoted to a gold or graphite layer can be increased. It has been empirically determined that covering less than 25 percent of the glass substrate with the conductive material represents a good compromise for EC devices that exhibit both rapid response times and acceptable transparency.

[0075] As noted above, highly conductive carbon (such as graphite) based counter-electrodes can also be employed. A first embodiment of a highly conductive carbon based counter-electrode is shown in FIGS. 7A and 7B. Once again, a preferred substrate is a polished float glass cuvette plate, about 0.7 mm thick. An ITO coating 64 is applied on one side of the polished float glass cuvette plate, and a carbon coating 62 is then applied over the ITO coating. Preferably, the highly conductive carbon material is graphite (HITASOL GA.66M). The electrical conductivity of this highly conductive carbon material is known to be not less than 10⁻² S/cm. Preferably, less than 25 percent of the glass substrate is covered with the carbon, in order to maintain high transmittance. While lithography and sputtering were employed for gold patterning on glass substrate as described above, screen printing was employed for forming a graphite pattern on a glass substrate for the highly conductive carbon-based counter-electrode. It is anticipated that because screen printing technology requires less expensive equipment than does lithography and sputtering techniques, that mass production of highly conductive carbon-based counter-electrodes may be less expensive than mass production of gold-based counter-electrodes.

[0076] Note that in this embodiment of a graphite based counter-electrode, the glass substrate is coated with indium tin oxide on one side to form a transparent insulating substrate for the counter-electrode. Because the electric conductivity of gold is much higher than that of graphite, gold can be directly deposited on the glass substrate without ITO glass, but it is preferable to deposit a graphite pattern onto an ITO layer. While less preferred, it should be noted that an acceptable graphite based counter-electrode can be fashioned without the ITO layer illustrated in FIG. 7B.

[0077] Preferably, each polymer layer within these laminated devices are on the order of 150 nanometers in thickness, each solid electrolyte layer is approximately 30 microns in thickness, and the gold patterned layer on the counter-electrode is on the order of 50-100 nanometers in thickness. A preferable range of thickness for a graphite layer in a counter-electrode is also 50-100 nanometers, more preferably 100 nanometers. A preferred thickness for an ITO film is from about 10 nanometers to about 200 nanometers, with more electrical conductivity being provided by a thicker layer. Thus electrical conductivity within an EC device can be manipulated by adjusting a thickness of the ITO layer, especially an ITO layer employed in a counter-electrode. A preferred thickness for a transparent substrate (such as glass or plastic) utilized in a transparent electrode (or counter-electrode) is about 0.5-1.0 millimeters, most preferably 0.7 millimeters.

[0078] A platinum wire has been successfully employed as a counter-electrode in an EC device generally corresponding to the second configuration as shown in FIGS. 4A and 4B. While EC devices having a configuration (i.e., a cathodic EC polymer, a solid electrolyte layer, and a non EC polymer counter-electrode) preferably employ PProDOT-Me₂ as the cathodic layer, it should be understood that other EC cathodic polymers can be beneficially employed. It should be understood that a single polymer EC device can be fashioned using a counter-electrode and an anodic EC polymer, as opposed to a counter-electrode and a cathodic EC polymer. A single polymer EC device fashioned using a counter-electrode and an anodic EC polymer would be less transparent (i.e. the anodic EC polymer layer would be in its darker state) with no voltage (or a positive voltage) applied, and as a negative voltage is applied to the such as EC device the anodic EC polymer layer would transition to its more transparent state. This is the opposite of a single polymer EC device fashioned using a counter-electrode and a cathodic EC polymer, which is more transparent without a voltage (or a positive voltage) being applied, and become more opaque as a negative voltage is applied.

[0079] A sample device based on the single polymer/counter-electrode EC device described above was constructed using rectangular layers substantially 7 mm×50 mm. An ITO coated 7 mm×50 mm glass slide was prepared for the transparent electrode, and a layer of PProDOT-Me₂ was deposited on the ITO coated surface. A glass wafer onto which a grid pattern of gold had been deposited was cut into 7 mm×50 mm plates. Similar 7 mm×50 mm plates of graphite deposited in a grid pattern were also prepared. A PMMA/LiClO₄ gel electrolyte was uniformly placed between the cathodic EC polymer deposited on the ITO slide and the counter-electrode to form a layered device. Two devices were prepared, one with a gold counter-electrode, and one with a graphite counter-electrode layer. The graphite based counter-electrode differs from the gold based counter-electrode in that a layer of ITO was first placed on the glass substrate before the graphite was deposited, while no such layer was employed in the gold based counter-electrode. A rubber sealant was employed, and the assembled devices were allowed to cure for about 20 hours. It is anticipated that additional curing time might be beneficial, and that 20-30 hours represents a preferred range of cure times. The sealant employed was a parafilm, a readily available, semi-transparent, flexible thermoplastic sealant. A schematic illustration of these working models is provided in FIGS. 8A and 8B. it should be noted that the working models are consistent with the second embodiment discussed above with respect to FIGS. 4A and 4B. As above, the schematic model is shown in both an oxidized state (no voltage or a positive voltage applied) and a reduced state (a negative voltage applied).

[0080]FIG. 8A schematically shows a cross-sectional view and a top plan view of a working model in an oxidized state (no voltage or positive voltage applied). The cross-sectional view clearly shows the top layer as being transparent electrode 42, which was prepared by coating glass slide with ITO. Immediately adjacent to transparent electrode 42 is transparent layer 44 a, a thin film of the cathodic PProDOT-Me₂ EC polymer coated onto the transparent electrode 42. The next layer includes a generally circular solid/gel electrolyte layer 46, which is surrounded by a sealant 53 to prevent any of the electrolyte from leaking. As discussed above, the solid electrolyte layer (and sealant) is followed by counter-electrode layer 52. Note that shape of the solid electrolyte layer defines that area of the EC polymer layer that will change color. Portions of the EC polymer layer that are not in contact with the electrolyte layer will not undergo a change in color. In the present example, the EC polymer layer coated the entire generally square shaped transparent substrate, the sealant was applied as a generally circular mask (i.e. the sealant was applied over the entire surface of the EC polymer layer except for a generally circular portion where no sealant was applied) and the solid electrolyte layer was deposited within the generally circular portion defined by the sealant mask. A quite sharp demarcation between portions of the EC polymer immediately adjacent to the solid electrolyte layer (such portions transitioning from a light state to a dark state under an applied negative voltage) was achieved relative to portions of the EC polymer layer immediately adjacent to the sealant (i.e. not immediately adjacent to the solid electrolyte layer, such portions not transitioning from a light state to a dark state under an applied negative voltage). Very little bleed though occurred at the interface between the sealant and the solid electrolyte layer, enabling a sharply defined window (i.e. the portion of the EC polymer layer that transitioned from light to dark under an applied negative voltage) to be achieved. Of course, the sealant mask and electrolyte area can be combined in shapes other than the generally circular shape employed here. Whatever shape the sealant can be conformed into can be used to define a window corresponding to the inverse of that shape, by filling the inverse (i.e. the void) with the electrolyte. Note that no bottom transparent electrode layer is required. FIG. 8B shows the working model after a negative voltage has been applied, and the portion of the EC polymer layer in contact with electrolyte has changed color, while the balance of the EC polymer layer (i.e. the portion in contact with the sealant) has not. With respect to FIGS. 8A and 8B, as noted above, the polarity of the voltage applied determines how such devices will respond.

[0081] Experimental Results

[0082] Electrochemical empirical studies were carried out with working samples corresponding to the second configuration as illustrated in FIGS. 4A and 4B. PProDOT-Me₂ was employed as the cathodic EC polymer, and a platinum wire was employed as the counter-electrode. The studies were executed using an potentiostat/galvanostat electrochemical analyzer, CH 1605A, from CH Instruments, with silver (Ag/Ag⁺) as the reference electrode, an ITO-coated one-glass slide as the working electrode, and a platinum (Pt) wire as the counter-electrode. The electrolyte employed (in this case, a liquid electrolyte) was 0.1N TBAP/ACN. Spectro-electrochemistry was carried out on a Varian Corp. UV-Vis-NIR spectrophotometer. FIGS. 8 and 9 graphically illustrate the fast and repeatable actuation of each of the EC devices described above. In particular, FIG. 9A provides switching data for an EC device with a PProDOT-Me₂ cathodic layer, an electrolyte layer, and a counter-electrode layer, while FIG. 9B provides switching data for an EC device with a PProDOT-Me₂ cathodic layer, an electrolyte layer, and a PBEDOT-NMeCz anodic layer.

[0083] For optical switching studies, devices based on a PProDOT-Me₂ cathodic layer, an electrolyte layer, and a gold counter-electrode layer, and a PProDOT-Me₂ cathodic layer, an electrolyte layer, and a graphite counter-electrode layer were used. Again, spectro-electrochemistry was carried out on an UV-vis spectrophotometer. High contrast ratios in visible region were observed for gold based counter-electrode device, as is graphically indicated in FIG. 10A. The high contrast ratios are attributed to the high transmittance of Au-based counter-electrode and the cathodic EC polymer in the oxidized state.

[0084] The colored state of graphite based counter-electrode device shown in FIG. 10B was somewhat darker than gold based counter-electrode device, but the bleached state of the graphite based counter-electrode device was also darker, due to the lower percentage transmittance through the graphite based counter-electrode layer.

[0085] Optical switching is an important characteristic of an EC device, and each device, based on gold and graphite counter-electrodes, were tested for switching. FIG. 11A graphically illustrates the results for the gold based counter-electrode device, while FIG. 11B graphically illustrates the results for the graphite-based counter-electrode device, based on absorbance under a wavelength of 580 nm and an application of 2.0V. Each device exhibited good repeatability and a rapid change in absorbance. The percentage transmittance in the bleached state of the graphite based counter-electrode device was lower than gold based counter-electrode device, but the absorbance response to potential is more rapid in graphite based counter-electrode device. This result is likely due to the fact that graphite, whose electric conductivity is lower than that of gold, was patterned on ITO for enhancement of the overall conductivity.

[0086] For each device, the colors reached equilibrium within almost the same time (less than 1 second), even at the different applied potentials, as is graphically indicated in FIG. 12, with respect to the gold based counter-electrode device. Note that the color saturation (i.e. the degree of opacity) is dependent upon the magnitude of the potentials applied, as is graphically indicated in FIG. 13, with respect to the gold based counter-electrode device. While FIGS. 12 and 13 only refer to the gold based counter-electrode device, the graphite-based counter-electrode device behaved similarly.

[0087] It is believed that the redox reaction occurs just on the surface of EC polymer film, and that the doping reaction requires very small amount of ions. This property of the EC devices was studied using an potentiostat/galvanostat electrochemical analyzer, CH 1605A, from CH Instruments. By connecting the counter-electrode and the reference electrode to the above analyzer with gold (or graphite) patterned glass slide as a counter-electrode, electrochemical data of an EC polymer-deposited ITO glass slide as the working electrode were measured. FIG. 14A graphically illustrates the repeatability of performance during the oxidization and reduction reactions of gold based counter-electrode device, while FIG. 14B shows the same result for the graphite-based counter-electrode device, upon varying polarity of a constant potential (i.e., 2.0 volts). Each device exhibited very stable repeatability within 1 second, a rapid response time. Under the same potential, the magnitude of the current of the graphite-based counter-electrode device was twice that of the gold based counter-electrode. This result is due to the high electric conductivity of the graphite-based counter-electrode, resulting in a color change response time that is shorter than that of the gold based counter-electrode device. This fact is apparent in FIG. 11B, where the absorbance vs. time curve of the graphite-based counter-electrode device has a very steep slope.

[0088] Temperature dependence of the color change performance of EC materials is also an important factor in designing EC devices. The magnitude of electric current of EC devices under the application of constant voltage represents color change property of the devices. The devices (gold and graphite based counter-electrodes) were analyzed in a Temperature& Humidity Chamber (PDL-3K, ESPEC). Current time curves were measured by a potentiostat/galvanostat electrochemical analyzer at a constant 2.0 volts under various temperatures in the chamber. FIG. 15 graphically illustrates a plot of the maximum electric current in each EC device as a function of temperature. Current of the gold based counter-electrode device increased very slightly within a temperature range of −40 to 10° C., but it became stable in the high temperature range of 10-80° C., while the graphite-based counter-electrode device was more stable over the entire range. The maximum current change for either device was less than 2×10⁻³ mA from −40 to 100° C.

[0089] The speed of the switching between transparent and colored states of both the gold based counter-electrode device and the graphite-based counter-electrode device is rapid, occurring in the range of about 0.3-1.0 seconds. The graphite-based counter-electrode device using ITO in the counter-electrode can achieve a 0.3-0.8 second response time, upon an applied 2 volts potential, and is repeatable (10,000 times). That performance is faster than achieved in the gold based counter-electrode device (which did not use ITO in the counter-electrode). The gold based counter-electrode device achieved a higher percentage change in transmittance between the transparent and opaque states. The power consumption of the devices are modest, 2-2.5 volts times 10-20 mA. The temperature range under which the switching is stable is a relatively wide, −40° C. ˜100° C. In addition, the weight of the devices are minimal. The gold based counter-electrode device and the graphite-based counter-electrode device exhibit good perceived contrast, require a low switching voltage, and hence, are of special interest for use in dialed-tint windows, large areas display, antiglare car rear-view mirrors, and other applications where controllable color switching is useful.

[0090] Specific Applications

[0091] Yet another aspect of the present invention relates to specific applications for EC devices. In a first embodiment, an EC device including a PBEDOT-NMeCz anodic layer is employed as a display. Because PBEDOT-NMeCz has a yellowish tint in the oxidized state, and a blue tint in the reduced state, a multicolor display can be achieved. Such an EC device preferably includes a plurality of pixels, each pixel being defined by an individually addressable grid of a dual polymer EC device including a PBEDOT-NMeCz anodic layer. A voltage can be applied to each pixel individually, enabling a flat panel display to be achieved in which the color of each pixel is separately controlled.

[0092] Still another application specific embodiment is directed to a DW for DNA chip reading technology based on SPR imaging with high lateral resolution. SPR imaging is an accepted technology, which currently utilizes expensive custom photomasks. In this embodiment, a DW including a plurality of individually addressable pixels arranged in a grid format is employed in the place of the conventional photomask. The DW includes a plurality of individual pixels, each of which is a laminated EC such as the dual polymer and single polymer devices described above. A voltage can be applied to each pixel individually, enabling selective masking to be achieved, pixel by pixel. Thus a DW provides a switchable window, from transparent to non-transparent (dark blue) by varying electric potential polarity. The laminated EC devices described above are fabricated in a digital (pixel) array, whose size are typically 0.5-50 microns across.

[0093] The impact of the above described DW technology is expected to be multifold and immediately transferable to DNA array chip technology, particularly the technology for reading unknown DNA and unknown molecules (in vitro or in vivo) by using SPR. An example of using a preferred embodiment of a DW in accord with the present invention is shown in FIG. 16. In FIG. 16, a DW/SPR imaging system 100 includes a conventional SPR imaging system in which DW 102 is inserted. Conventional elements of DW/SPR imaging system 100 include a flow cell 104, a patterned analytic layer 106, a gold or silver layer 108, a laser light source 110 for directing light to the analytic layer along a first path 112, a first optical element 114 disposed in first light path 112 (for polarizing the light from light source 110), a prism 116 disposed in first light path 112 and adjacent to the analytic layer, such that light traveling along first light path 112 passes through the prism. A second optical element 118 is disposed along a second light path 120, and a charge coupled device (CCD) detector 122 disposed in second light path 120 to receive light focused by second optical element 118. Not separately shown are a plurality of electrical conductors coupled to each pixel of the DW, such that a voltage can be individually applied to each pixel, and a power supply electrically coupled to the electrical conductors and the laser light source.

[0094] By combining a DW with a conventional SPR imaging systems that has been used as a real time analyzer of unknown molecules, including DNAs and RNAs, a new SPR system with high spatial resolution is achieved. The high resolution DW/SPR system is expected to analyze unknown molecules and DNAs on a real-time basis at a faster speed rate than can be achieved by conventional SPR imaging systems, by scanning through one group of molecules to another by opening the corresponding several pixels in digital window. The DW can be left in place, and reconfigured by activating different pixels. In contrast, a photomask would have to be removed and replaced with a different mask to achieve a different masking pattern.

[0095] Yet another aspect of the present invention is a smart window that can be used in structural and architectural applications, such as in cars, planes, and buildings. Such a smart window is able to change state from being substantially transparent in a first state, with no voltage (or a positive voltage) applied, to being substantially opaque in a second state, with a negative voltage applied. FIG. 17 illustrates single or dual polymer EC devices such as those described above being incorporated into a conventional dual pane window 130. Note that FIG. 17 includes a front view, a side view, and an expanded portion view, each of which is appropriately labeled. Smart windows differ from conventional windows in that the EC device layered between conventional glass outer pane 134 and inner pane 136, enables wires (not separately shown) extending from the smart window to be coupled to a controllable voltage source, such that the smart window will transition from being generally transparent to being significantly less transparent. If a void or gap 140 separates the panes of conventional glass, preferably the EC device is coupled to outer pane 134, rather than inner pane 136. A first embodiment of a smart window is based on a dual polymer EC device using a ProDOT-Me₂ cathodic polymer layer, a solid electrolyte layer, and a PBEDOT-NMeCz anodic polymer layer, as described above. A second embodiment of a smart window is based on a single polymer EC device, using a PProDOT-Me₂ cathodic polymer layer, a solid electrolyte layer, and a counter-electrode layer, substantially as described above.

[0096] Because the dual and single polymer EC devices described above exhibit good perceived contrast and require a low switching voltage, they are anticipated to be of special interest in other applications as well, such as large area displays, automatic mirrors, and other applications where color change in response to an applied voltage desirable.

[0097] Overview of Paired PProDOT-Me₂ & Counter-Electrode Functionality

[0098] PProDOT-Me₂ can be used as a cathodically coloring polymer. PProDOT-Me₂ is dark blue color in its fully reduced form, and a very transmissive light blue in its fully oxidized form. This cathodically coloring polymer changes from a light color to a highly colored state upon charge neutralization (i.e. reduction) of the p-doped form. The π-π* transition is depleted at the expense of transitions outside the visible region. Therefore, the dominant wavelength of the color is the same throughout the doping process. The EC process of an EC device utilizing a PProDOT-Me₂ cathodic layer, a gel electrolyte containing lithium perchlorate (LiClO₄), and a gold based counter-electrode is illustrated in FIG. 17, where the gold layer plays the role of the second layer required in the paired layer process explained below.

[0099] The EC process requires paired layers, with the PProDOT-Me₂ layer acting as a first one of the paired layers, and the gold based counter-electrode acting as a second one of the paired layers. In the left side of FIG. 18, a negative voltage has been applied and the PProDOT-Me₂ polymer is in its reduced, highly blue colored state. The gold based counter-electrode layer is attracting the negatively charged perchlorate (ClO₄) ions. In the right side of FIG. 18, no voltage (or a positive voltage) is being applied. and the PProDOT-Me₂ polymer is in its oxidized, p-doped light color state. The gold based counter-electrode layer is attracting positively charged lithium (Li) ions.

[0100] The gel electrolyte separating the PProDOT-Me₂ polymer layer and the gold based counter-electrode layer is ionically conductive but electronically insulating, so the lithium and perchlorate ions are mobile and free to move between the PProDOT-Me₂ polymer side and the gold based counter-electrode side under polarity change of applied potential.

[0101] The graphite based counter-electrode works by the same mechanism. This electric double layer results in no chemical reaction, and causes no structural change in the counter-electrode layer (gold or graphite). The electric double layer can store both negative and positive charges.

[0102] Although the present invention has been described in connection with the preferred form of practicing it, those of ordinary skill in the art will understand that many modifications can be made thereto within the scope of the claims that follow. Accordingly, it is not intended that the scope of the invention in any way be limited by the above description, but instead be determined entirely by reference to the claims that follow. 

The invention in which an exclusive right is claimed is defined by the following:
 1. A method for synthesizing an electrochromic polymer suitable for use as a cathodic layer within a laminated electrochromic device; comprising the steps of: (a) providing a first quantity of 3,4-dimethoxythiophene and a second quantity of 2,2-dimethyl-1,3-propanediol; (b) dissolving the first and second quantities in a sufficient quantity of toluene, such that substantially all of the first and second quantities dissolve in the toluene to form a solution; and (c) refluxing the solution for at least eight hours, such that: (i) the solution boils; (ii) the toluene vaporizes, condenses and returns to the solution; and (iii) the first and second quantities react to form [3,3-dimethyl-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepine].
 2. The method of claim 1, wherein the step of heating the solution comprises the step of heating the solution to a temperature of about one hundred ten degrees Celsius.
 3. The method of claim 1, wherein the step of providing a first quantity of 3,4-dimethoxythiophene and a second quantity of 2,2-dimethyl-1,3-propanediol comprises the step of providing substantially equivalent molar amounts of 3,4-dimethoxythiophene and 2,2-dimethyl-1,3-propanediol.
 4. The method of claim 1, further comprising the step of adding a catalyst to the solution before the step of refluxing the solution.
 5. The method of claim 4, wherein the step of adding a catalyst comprises the step of adding p-toluenesulfonic acid to the solution.
 6. The method of claim 5, wherein the step of adding p-toluenesulfonic acid to the solution comprises the step of adding a quantity of p-toluenesulfonic acid comprising less than 10 percent of a molar equivalent of the first quantity of 3,4-dimethoxythiophene that is dissolved in the toluene.
 7. The method of claim 5, wherein the quantity of p-toluenesulfonic acid added to the solution comprises substantially 1.5 percent of a molar equivalent of the first quantity of 3,4-dimethoxythiophene that is dissolved in the toluene.
 8. The method of claim 1, further comprising the step of adding calcium chloride to the condensed toluene before returning the condensed toluene to the solution, to remove a methanol byproduct from the condensed toluene.
 9. A method for synthesizing an electrochromic polymer suitable for use as an anodic layer within a laminated electrochromic device; comprising the steps of: (a) producing a first intermediate reagent by: (i) providing a first quantity of (3,4-ethylenedioxythiophene) (EDOT), a second quantity of n-butyl lithium; and a third quantity of chilled tetrahydrofuran (THF), the third quantity being sufficient to substantially dissolve the first and second quantities; (ii) introducing the first and second quantities into the chilled THF to form a first solution; (iii) maintaining the first and second quantities in the chilled THF for a time sufficient to produce a Grignard reagent; and (iv) treating the Grignard reagent with a quantity of magnesium bromide diethyl etherate sufficient to produce a brominated compound, the brominated compound comprising the first intermediate reagent; (b) producing a second intermediate reagent by: (i) providing a fourth quantity of a dibromocarbazole, a fifth quantity of lithium hydride; and a sixth quantity of dimethyl foramide (DMF), the sixth quantity being sufficient to substantially dissolve the fourth and fifth quantities; (ii) introducing the fourth and fifth quantities into the DMF to form a second solution; (iii) cooling the second solution below room temperature; and (iv) methylating the dibromocarbazole to produce a methylated dibromocarbazole intermediate product, the methylated dibromocarbazole intermediate product comprising the second intermediate reagent; and (c) combining the first and second intermediate reagents in the presence of a catalyst to produce [3,6-bis(2-(3,4-ethylenedioxythiophene))-N-methylcarbazole.
 10. The method of claim 9, wherein the step of methylating the dibromocarbazole comprises the step of adding methyl iodine to the second solution.
 11. The method of claim 9, wherein the step of providing a third quantity of chilled tetrahydrofuran (THF) comprises the step of providing the third quantity at a temperature of less than 0° C.
 12. The method of claim 9, wherein the step of maintaining the first and second quantities in the chilled THF for a time sufficient to produce a Grignard reagent comprises the step of maintaining the first and second quantities in the chilled THF for about one hour.
 13. The method of claim 9, wherein the step of methylating the second solution comprises the step of slowly increasing the temperature of the second solution for substantially two hours.
 14. The method of claim 9, further comprising the step of purifying the second intermediate reagent before combining the first and second intermediate reagents.
 15. The method of claim 14, wherein the step of purifying the second intermediate reagent comprises the steps of washing the second intermediate reagent with water, washing the second intermediate reagent with ether, and drying the second intermediate reagent with sodium sulfate.
 16. The method of claim 9, wherein the step of combining the first and second intermediate reagents comprises the steps of adding the second intermediate reagent to the first solution containing the first intermediate reagent and THF to form a third solution, adding a catalyst to the third solution, and maintaining the third solution at a temperature of about 50° C. for a period of about twelve hours.
 17. The method of claim 9, wherein the catalyst comprises nickel.
 18. A method of making a counter-electrode useful in an electrochromic device including a cathodic polymer layer; comprising the steps of: (a) providing a substantially transparent non-conductive substrate and a conductive material; and (b) depositing a patterned layer of the conductive material onto the non-conductive substrate, such that the patterned layer does not reduce a transmittance of the transparent non-conductive substrate by more than about twenty five percent.
 19. The method of claim 18, wherein the conductive material comprises gold, further comprising the step of depositing a layer comprising titanium-tungsten (TiW) on the substantially transparent non-conductive substrate before depositing the patterned layer of gold.
 20. The method of claim 18, wherein the conductive material comprises highly conductive carbon, further comprising the step of depositing a layer comprising a substantially transparent electrode on the substantially transparent non-conductive substrate before depositing the patterned layer of highly conductive carbon.
 21. The method of claim 20, wherein the substantially transparent electrode comprises a layer of indium tin oxide.
 22. The method of claim 18, wherein the patterned layer comprises a grid.
 23. The method of claim 18, wherein the patterned layer covers less than 25 percent of the surface of the substantially transparent non-conductive substrate.
 24. The method of claim 18, wherein the patterned layer is deposited using masking and sputtering techniques.
 25. A counter-electrode useful in an electrochromic device including a cathodic polymer layer; comprising: (a) a substantially transparent and substantially non-conductive substrate; and (b) a conductive material deposited onto the substrate in a patterned layer, such that the patterned layer does not reduce a transmittance of the transparent non-conductive substrate by substantially more than 25 percent.
 26. The counter-electrode of claim 25, wherein the conductive material comprises gold, further comprising a layer comprising titanium-tungsten (TiW) disposed between the substrate and the gold.
 27. The counter-electrode of claim 25, wherein the conductive material comprises highly conductive carbon, further comprising a layer comprising a transparent electrode disposed between the substrate and the highly conductive carbon.
 28. The counter-electrode of claim 27, wherein the transparent electrode comprises indium tin oxide.
 29. The counter-electrode of claim 25, wherein the patterned layer comprises a grid.
 30. The counter-electrode of claim 25, wherein the patterned layer covers less than 25 percent of the surface of the substrate.
 31. A laminated electrochromic device comprising: (a) a first layer comprising a transparent electrode; (b) a cathodic polymer layer comprising poly[3,3-dimethyl-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepine]; (c) an electrolyte layer comprising a solid electrolyte; (d) an anodic polymer layer comprising poly[3,6-bis(2-(3,4ethylenedioxythiophene))-N-methylcarbazole; and (e) another electrode layer comprising a transparent electrode.
 32. The laminated electrochromic device of claim 31, wherein each transparent electrode comprises a glass substrate coated with indium tin oxide.
 33. The laminated electrochromic device of claim 31, wherein the solid electrolyte comprises a gel electrolyte, said gel electrolyte comprising: (a) a polymer matrix; (b) a solvent carrier; and (c) a source of ions.
 34. The laminated electrochromic device of claim 33, wherein a source of ions comprises a lithium salt.
 35. The laminated electrochromic device of claim 33, wherein the source of ions comprises tetrabutyl ammonium perchlorate.
 36. The laminated electrochromic device of claim 33, wherein the polymer matrix comprises poly vinyl chloride.
 37. The laminated electrochromic device of claim 33, wherein the polymer matrix comprises poly methyl methacrylate.
 38. The laminated electrochromic device of claim 33, wherein the solvent comprises acetonitrile.
 39. The laminated electrochromic device of claim 33, wherein the solvent comprises at least one of ethylene carbonate and propylene carbonate.
 40. A laminated electrochromic device comprising: (a) a transparent electrode layer; (b) a cathodic polymer layer; (c) an electrolyte layer comprising a solid electrolyte; and (d) a counter electrode layer.
 41. The laminated electrochromic device of claim 40, wherein the transparent electrode layer comprises a glass substrate coated with indium tin oxide.
 42. The laminated electrochromic device of claim 40, wherein the cathodic polymer layer comprises poly[3,3-dimethyl-3,4-dihydro-2H-thieno[3,4-b]-[1,4]dioxepine].
 43. The laminated electrochromic device of claim 40, wherein the solid electrolyte comprises a gel electrolyte, said gel electrolyte comprising: (a) a polymer matrix; (b) a solvent carrier; and (c) a source of ions.
 44. The laminated electrochromic device of claim 43, wherein the source of ions comprises at least one of a lithium salt and tetrabutyl ammonium perchlorate.
 45. The laminated electrochromic device of claim 43, wherein the polymer matrix comprises at least one of poly vinyl chloride and poly methyl methacrylate.
 46. The laminated electrochromic device of claim 43, wherein the solvent comprises at least one of acetonitrile, ethylene carbonate and propylene carbonate.
 47. The laminated electrochromic device of claim 40, wherein the counter-electrode comprises: (a) a transparent non-conductive substrate; and; (b) a conductive material deposited onto the non-conductive substrate in a patterned layer, such that the patterned layer does not reduce a transmittance of the transparent electrode layer by more than about 25 percent.
 48. The laminated electrochromic device of claim 47, wherein the conductive material comprises gold, further comprising a titanium-tungsten (TiW) layer disposed between the transparent electrode layer and the gold.
 49. The laminated electrochromic device of claim 47, wherein the conductive material comprises highly conductive carbon.
 50. The laminated electrochromic device of claim 47, wherein the transparent electrode layer comprises indium tin oxide.
 51. The laminated electrochromic device of claim 47, wherein the patterned layer comprises a grid.
 52. The laminated electrochromic device of claim 47, wherein the patterned layer covers less than about 25 percent of the surface of the transparent electrode layer.
 53. A dual polymer electrochromic window suitable for architectural and structural applications, comprising: (a) a first layer comprising a structural glass panel; (b) a second layer comprising a transparent electrode; (c) a third layer comprising a cathodic polymer layer of poly[3,3-dimethyl-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepine]; (d) a fourth layer comprising a transparent solid electrolyte; (e) a fifth comprising an anodic polymer layer of poly[3,6-bis(2-(3,4ethylenedioxythiophene))-N-methylcarbazole; (f) a sixth layer comprising a transparent electrode; (g) a seventh layer comprising a structural glass panel; (h) a first electrical lead coupled to the second layer; and (i) a second electrical lead coupled to the sixth layer, said first and second electrical leads applying a voltage to the second through sixth layers when coupled to a voltage source, said voltage causing the third and fifth layers to change colors.
 54. The dual polymer electrochromic window of claim 53, further comprising a gap filled with an inert gas that is disposed between said sixth and seventh layers.
 55. A single polymer electrochromic window suitable for architectural and structural applications, comprising: (a) a first layer comprising a structural glass panel; (b) a second layer comprising a transparent electrode; (c) a third layer comprising a cathodic polymer of poly[3,3-dimethyl-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepine]; (d) a fourth layer comprising a transparent solid electrolyte; (e) a fifth layer comprising a counter-electrode; (f) a sixth layer comprising a structural glass panel; (h) a first electrical lead coupled to the second layer; and (i) a second electrical lead coupled to the fifth layer, said first and second electrical leads applying a voltage to the second through fifth layers when coupled to a voltage source, said voltage causing the third layer to change color.
 56. The single polymer electrochromic window of claim 55, wherein the cathodic polymer layer comprises poly[3,3-dimethyl-3,4-dihydro-2H-thieno[3,4-b]-[1,4]dioxepine].
 57. The single polymer electrochromic window of claim 55, further comprising a gap filled with an inert gas that is disposed between said fifth and sixth layers.
 58. The single polymer electrochromic window of claim 55, wherein the counter-electrode comprises: (a) a transparent non-conductive substrate; and (b) a conductive material deposited onto the non-conductive substrate in a patterned layer, such that the patterned layer does not reduce a transmittance of the transparent non-conductive substrate by more than about 25 percent.
 59. The single polymer electrochromic window of claim 58, wherein the conductive material comprises gold, further comprising a layer comprising a titanium-tungsten (TiW) layer disposed between the transparent non-conductive substrate and the gold.
 60. The single polymer electrochromic window of claim 58, wherein the conductive material comprises highly conductive carbon.
 61. The single polymer electrochromic window of claim 58, wherein the patterned layer comprises a grid.
 62. A digital window suitable for use with pixilated addressing, comprising: (a) a digital window including a plurality of individually addressable pixels arranged in a grid format, each pixel being switchable between a transparent state and non-transparent state by selectively applying a voltage thereto, each pixel comprising a laminated electrochromic structure having a cathodic electrochromic polymer layer; and (b) a plurality of electrical conductors coupled to each pixel, such that a voltage can be individually applied to each pixel.
 63. The digital window of claim 62, wherein each pixel is less than about 50 microns in size.
 64. The digital window of claim 62, wherein each laminated electrochromic structure comprises: (a) a transparent electrode; (b) a cathodic polymer layer; (c) an electrolyte layer comprising a solid electrolyte; (d) an anodic polymer layer; and (e) another transparent electrode.
 65. The digital window of claim 64, wherein the cathodic polymer layer comprises poly[3,3-dimethyl-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepine].
 66. The digital window of claim 64, wherein the anodic polymer layer comprises poly[3,6-bis(2-(3,4ethylenedioxythiophene))-N-methylcarbazole.
 67. The digital window of claim 62, wherein each laminated electrochromic structure comprises: (a) a first layer comprising a transparent electrode; (b) a second layer comprising a cathodic polymer layer; (c) a third layer comprising a solid electrolyte; and (d) a fourth layer comprising a counter-electrode.
 68. The digital window of claim 67, wherein the cathodic polymer layer comprises poly[3,3-dimethyl-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepine].
 69. The digital window of claim 67, wherein the counter-electrode comprises: (a) a transparent non-conductive substrate; and (b) a conductive material deposited on the non-conductive substrate in a patterned layer, such that the patterned layer does not reduce a transmittance of the transparent non-conductive substrate by more than about 25 percent.
 70. The digital window of claim 69, wherein the conductive material comprises gold, further comprising a layer comprising a titanium-tungsten (TiW) layer disposed between the transparent non-conductive substrate and the gold.
 71. The digital window of claim 69, wherein the conductive material comprises highly conductive carbon.
 72. The digital window of claim 69, wherein the patterned layer comprises a grid.
 73. A surface plasmon resonance imaging system, comprising: (a) a flow cell; (b) a patterned analytic layer; (c) a light source directing light to the analytic layer along a first path; (d) a first optical element in the first path that polarizes the light; (e) a digital window disposed in the first path, the digital window including a plurality of individually addressable pixels arranged in a grid format, each pixel being switchable between a transparent state and a non-transparent state by applying a voltage thereto, each pixel comprising a laminated electrochromic structure having a cathodic electrochromic polymer layer, such that the digital window can selectively control whether light from the light source traveling along the first path reaches the analytic layer; (f) a plurality of electrical conductors coupled to each pixel, such that a voltage can be individually selectively applied to each pixel; (g) a power supply electrically coupled to said electrical conductors and said light source; (h) a prism disposed in the light path and adjacent to the analytic layer, such that light traveling along the first path passes through the prism; (i) a second optical element disposed along a second path, said optical element focusing light traveling from said analytic surface and passing the light that is focused through said prism; and (j) a detector disposed in the second path, said detector receiving light focused by the second optical element.
 74. The surface plasmon resonance imaging system of claim 73, wherein each pixel of the digital window is less than about 50 microns in size.
 75. The surface plasmon resonance imaging system of claim 73, wherein each laminated electrochromic structure of the digital window comprises: (a) a first layer comprising a transparent electrode; (b) a second layer comprising a cathodic polymer of poly[3,3-dimethyl-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepine]; (c) a third layer comprising a solid electrolyte; (d) a fourth layer comprising an anodic polymer of poly[3,6-bis(2-(3,4ethylenedioxythiophene))-N-methylcarbazole; and (e) a fifth layer comprising a transparent electrode.
 76. The surface plasmon resonance imaging system of claim 73, wherein each laminated electrochromic structure of the digital window comprises: (a) a first layer comprising a transparent electrode; (b) a second layer comprising a cathodic polymer of poly[3,3-dimethyl-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepine]; (c) a third layer comprising a solid electrolyte; and (d) a fourth layer comprising a counter-electrode.
 77. The surface plasmon resonance imaging system of claim 76, wherein the counter-electrode comprises: (a) a transparent non-conductive substrate; and; (b) a conductive material deposited onto the non-conductive substrate in a pattern, such that the patterned layer does not reduce a transmittance of the transparent non-conductive substrate by more than about 25 percent.
 78. The surface plasmon resonance imaging system of claim 76, wherein the conductive material comprises one of gold and highly conductive carbon.
 79. A multicolor display comprising: (a) a plurality of individually addressable pixels arranged in a grid format, each pixel being switchable between a transparent state and non-transparent state by applying a voltage, each pixel comprising a laminated electrochromic structure including a cathodic electrochromic polymer layer, at least some of the pixels further comprising an anodic polymer layer switchable between two different colors; and (b) a plurality of electrical conductors coupled to each pixel, such that a voltage can be selectively individually applied to each pixel.
 80. The multicolor display of claim 79, wherein the anodic polymer layer comprises poly[3,6-bis(2-(3,4ethylenedioxythiophene))-N-methylcarbazole. 